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In the title coordination polymer, [Pb(C5H2N2O4)(H2O)]n, the PbII atom is seven-coordinated by one N atom and five O atoms from four individual imidazole-4,5-dicarboxyl­ate (HIDC2−) groups and one water mol­ecule. It is inter­esting to note that the HIDC2− group serves as a bridging ligand to link the PbII atoms into a three-dimensional microporous open-framework.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106046415/bg3021sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106046415/bg3021Isup2.hkl
Contains datablock I

CCDC reference: 632930

Comment top

There has been considerable interest in the design and synthesis of metal–organic complexes during recent decades (Erxleben 2003). The structures and properties of such complexes depend on the coordination habits and geometric preferences of both metal ions and bridging ligands, as well as on the influence of weaker non-covalent interactions such as hydrogen bonding. In investigations of coordination polymers that address the use of bridging multidentate ligands, the anion of 1H-imidazole-4,5-dicarboxylic acid (H3IDC) exemplifies a ligand that is used in the formation of supramolecular complexes. This acid can be successively deprotonated to furnish H2IDC, HIDC2− and IDC3− anions, these anions giving rise to a wide range of supramolecular architectures. To our knowledge, some transition metal complexes with one-dimensional chain structures of Mn, Cu and Cd complexes (Zhang et al., 2004; Gao, Gu et al., 2004; Gao, Liu et al., 2004), two-dimensional layer structures of Mn and Fe complexes (Gao et al., 2005; Xu et al., 2004) and a three-dimensional Mn complex (Zhang et al., 2006) have been reported to date. Compared with the extensively investigated transition metal cordination polymers, it is surprising to see the relatively small number of main group metal coordination polymers. Recently,we have reported the structure of a mononuclear calcium complex (Gao, Zhang et al., 2004), and a two-dimensional brick-like layer barium coordination polymer (Zhang et al., 2005). However, no three-dimensional crystal structure of a main group metal coordination polymer constructed using this acid has yet been reported. We obtained the title novel three-dimensional lead(II) coordination polymer, [Pb(HIDC)(H2O)]n, (I), and its synthesis and crystal structure are reported here.

As shown in Fig. 1, the asymmetric building unit of complex (I) comprises one PbII atom, one HIDC2− dianion and one coordinated water molecule. Each PbII atom is seven-coordinated by one N atom of an HIDC2− anion, with a Pb—N distance of 2.491 (3) Å, five O atoms from four individual HIDC2− anions, with Pb—O distances in the range 2.474 (3)–2.822 (3) Å, and one water molecule, with a Pb—O distance of 2.739 (4) Å (Table 1). The PbII—O4iii [symmetry code: (iii) x + 1, −y + 1/2, z + 1/2] distance of 2.822 (3) Å is considerably longer, but lies within the range found for PbII—O bond distances in many similar PbII coordination polymers; for example, Morsali & Mahjoub (2004) reported a Pb—O range of 2.542 (10)–2.975 (9) Å.

It is interesting to note that each HIDC2− anion serves as a bridging ligand to link four PbII atoms into a three-dimensional microporous structure. The HIDC2− dianion in (I) shows four different coordination modes. Firstly, it binds to the Pb1 atom in an N,O-bidentate coordination mode through imidazole atom N1 and carboxyl atom O1, forming a five-membered chelate ring. Secondly, it coordinates to atom Pb1A [symmetry code: (A) x, −y + 1/2, z − 1/2] in an O,O-bidentate coordination mode through two carboxyl atoms, O2 and O3, generating a seven-membered chelate ring with an envelope-like conformation. Thirdly, it bridges atoms Pb1A and Pb1B [symmetry code: (B) −x + 1, y + 1/2, −z + 1/2] through carboxyl atom O3. In this case, a centrosymmetric four-membered (Pb/O/Pb/O) loop is formed, with a Pb···Pb distance of 4.1523 (9) Å. Fourthly, it coordinates to atom Pb1C [symmetry code: (C) x − 1, −y + 1/2, z − 1/2] in a monodentate coordination mode through carboxyl atom O4. Furthermore, four such HIDC2− ligands connect four PbII centres, generating a macrocyclic ring structure, with adjacent PbII···PbII distances of 6.4103 (10) and 9.1379 (16) Å (Fig. 2). As a consequence of these H2IDC bridges, as well as the hydrogen bonds in which all active H atoms in the structure are involved (Table 2), polymer (I) presents an extended three-dimensional microporous open-framework.

Experimental top

Pb(NO3)2·4H2O (4.03 g, 10 mmol), 1H-imidazole-4,5-dicarboxylic acid (1.54 g, 10 mmol) and NaOH (0.8 g, 20 mmol) were dissolved in an aqueous solution (25 ml). The mixture was sealed in a 50 ml Teflon-lined stainless steel bomb and held at 403 K for 5 d. The bomb was cooled naturally to room temperature, and colourless prismatic crystals were obtained after several days. CHN analysis, calculated for C5H4N2O5Pb: C 15.83, H 1.06, N 7.39%; found: C 15.86, H 1.08, N 7.36%.

Refinement top

H atoms on C and N atoms were placed in calculated positions, with C—H = 0.93 Å and N—H = 0.86 Å, and were refined in the riding-model approximation, with Uiso(H) = 1.2Ueq(C,N). Water H atoms were located in a difference Fourier map and refined with O—H and H···H distance restraints of 0.85 (1) and 1.39 (1) Å, respectively, and with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A plot of the title complex, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x, −y + 1/2, z + 1/2; (ii) −x + 1, y − 1/2, −z + 1/2; (iii) x + 1, −y + 1/2, z + 1/2; (A) x, −y + 1/2, z − 1/2; (B) −x + 1, y + 1/2, −z + 1/2; (C) x − 1, −y + 1/2, z − 1/2.]
[Figure 2] Fig. 2. A packing diagram for (I), viewed down the a axis, showing the macrocyclic ring structure. H atoms have been omitted.
poly[aqua-µ-imidazole-4,5-dicarboxylato-lead(II)] top
Crystal data top
[Pb(C5H2N2O4)(H2O)]F(000) = 680
Mr = 379.30Dx = 3.345 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6840 reflections
a = 7.0301 (14) Åθ = 3.2–27.5°
b = 15.707 (3) ŵ = 22.39 mm1
c = 6.9680 (14) ÅT = 295 K
β = 101.77 (3)°Prism, colourless
V = 753.2 (3) Å30.28 × 0.22 × 0.12 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1717 independent reflections
Radiation source: fine-focus sealed tube1631 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 10.000 pixels mm-1θmax = 27.5°, θmin = 3.2°
ω scansh = 99
Absorption correction: numerical
(NUMABS; Higashi, 1995)
k = 2019
Tmin = 0.007, Tmax = 0.068l = 98
7289 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.049H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0251P)2 + 1.5416P]
where P = (Fo2 + 2Fc2)/3
1717 reflections(Δ/σ)max = 0.001
124 parametersΔρmax = 0.59 e Å3
3 restraintsΔρmin = 2.08 e Å3
Crystal data top
[Pb(C5H2N2O4)(H2O)]V = 753.2 (3) Å3
Mr = 379.30Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.0301 (14) ŵ = 22.39 mm1
b = 15.707 (3) ÅT = 295 K
c = 6.9680 (14) Å0.28 × 0.22 × 0.12 mm
β = 101.77 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1717 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 1995)
1631 reflections with I > 2σ(I)
Tmin = 0.007, Tmax = 0.068Rint = 0.037
7289 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0203 restraints
wR(F2) = 0.049H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.59 e Å3
1717 reflectionsΔρmin = 2.08 e Å3
124 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pb10.76575 (2)0.078709 (8)0.51318 (2)0.01682 (7)
O1W0.9412 (5)0.0560 (2)0.2002 (5)0.0322 (7)
H1W10.903 (9)0.084 (2)0.094 (4)0.048*
H1W20.889 (8)0.0068 (16)0.187 (7)0.048*
O10.8664 (4)0.22831 (17)0.4842 (4)0.0228 (6)
O20.8011 (4)0.35846 (16)0.3635 (4)0.0217 (6)
O30.4554 (5)0.44080 (18)0.1435 (5)0.0259 (7)
O40.1632 (5)0.4016 (2)0.1841 (6)0.0371 (8)
N10.5249 (5)0.16545 (19)0.2821 (5)0.0179 (6)
N20.2548 (5)0.2321 (2)0.1514 (5)0.0193 (7)
H60.13470.24020.09820.023*
C10.3387 (6)0.1570 (2)0.1992 (6)0.0205 (8)
H10.27460.10500.17720.025*
C20.7564 (6)0.2823 (2)0.3817 (5)0.0144 (7)
C30.5611 (5)0.2516 (2)0.2833 (5)0.0148 (7)
C40.3932 (6)0.2946 (2)0.2018 (5)0.0153 (7)
C50.3345 (6)0.3856 (2)0.1756 (6)0.0184 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb10.01287 (10)0.01455 (10)0.02209 (10)0.00133 (4)0.00136 (7)0.00108 (5)
O1W0.038 (2)0.0290 (14)0.0271 (15)0.0037 (15)0.0005 (14)0.0092 (14)
O10.0134 (14)0.0198 (12)0.0303 (14)0.0021 (11)0.0072 (12)0.0062 (12)
O20.0221 (16)0.0173 (12)0.0241 (13)0.0046 (11)0.0010 (12)0.0019 (11)
O30.0222 (17)0.0177 (12)0.0411 (17)0.0043 (12)0.0145 (14)0.0076 (13)
O40.0166 (17)0.0226 (14)0.073 (3)0.0049 (13)0.0117 (17)0.0041 (16)
N10.0139 (17)0.0162 (14)0.0215 (14)0.0012 (12)0.0017 (12)0.0014 (13)
N20.0116 (16)0.0198 (15)0.0237 (15)0.0003 (12)0.0035 (13)0.0015 (13)
C10.015 (2)0.0161 (16)0.0278 (19)0.0040 (15)0.0008 (16)0.0008 (15)
C20.0108 (18)0.0171 (16)0.0158 (15)0.0024 (13)0.0038 (14)0.0001 (14)
C30.0117 (18)0.0155 (15)0.0169 (15)0.0013 (13)0.0022 (14)0.0015 (14)
C40.0139 (19)0.0155 (16)0.0167 (16)0.0016 (14)0.0035 (14)0.0004 (14)
C50.0136 (19)0.0196 (17)0.0203 (17)0.0041 (15)0.0002 (15)0.0010 (15)
Geometric parameters (Å, º) top
Pb1—O12.474 (3)O3—C51.266 (5)
Pb1—N12.491 (3)O4—C51.243 (5)
Pb1—O3i2.547 (3)N1—C11.325 (5)
Pb1—O2i2.598 (3)N1—C31.377 (4)
Pb1—O1W2.739 (4)N2—C11.331 (5)
Pb1—O3ii2.758 (3)N2—C41.376 (5)
Pb1—O4iii2.822 (3)N2—H60.8600
O1W—H1W10.86 (3)C1—H10.9300
O1W—H1W20.85 (3)C2—C31.484 (5)
O1—C21.266 (5)C3—C41.378 (5)
O2—C21.250 (4)C4—C51.489 (5)
O1—Pb1—N166.16 (10)C5—O3—Pb1iv129.5 (3)
O1—Pb1—O3i115.05 (10)C5—O3—Pb1v105.3 (2)
N1—Pb1—O3i77.14 (11)Pb1iv—O3—Pb1v114.09 (11)
O1—Pb1—O2i75.03 (9)C1—N1—C3105.4 (3)
N1—Pb1—O2i108.78 (10)C1—N1—Pb1135.1 (2)
O3i—Pb1—O2i68.63 (10)C3—N1—Pb1115.7 (2)
O1—Pb1—O1W82.87 (10)C1—N2—C4108.3 (3)
N1—Pb1—O1W85.04 (10)C1—N2—H6125.8
O3i—Pb1—O1W145.67 (11)C4—N2—H6125.8
O2i—Pb1—O1W145.63 (10)N1—C1—N2111.6 (3)
O1—Pb1—O3ii149.44 (10)N1—C1—H1124.2
N1—Pb1—O3ii85.40 (10)N2—C1—H1124.2
O3i—Pb1—O3ii65.91 (11)O2—C2—O1124.1 (4)
O2i—Pb1—O3ii127.48 (9)O2—C2—C3119.5 (3)
O1W—Pb1—O3ii83.79 (9)O1—C2—C3116.4 (3)
O1w—Pb1—O4iii77.42 (10)N1—C3—C4109.7 (3)
O1—Pb1—O4iii69.82 (10)N1—C3—C2118.3 (3)
N1—Pb1—O4iii134.22 (10)C4—C3—C2131.7 (3)
O2i—Pb1—O4iii70.42 (10)N2—C4—C3104.9 (3)
O3i—Pb1—O4iii135.22 (10)N2—C4—C5119.3 (3)
O3ii—Pb1—O4iii133.12 (10)C3—C4—C5135.6 (4)
Pb1—O1W—H1W1121 (4)O4—C5—O3124.2 (4)
Pb1—O1W—H1W287 (4)O4—C5—C4115.8 (4)
C2—O1—Pb1122.0 (2)O3—C5—C4120.0 (4)
C2—O2—Pb1iv118.7 (2)H1W1—O1W—H1W2109 (4)
N1—Pb1—O1—C24.1 (3)C1—N1—C3—C40.6 (4)
O3i—Pb1—O1—C257.5 (3)Pb1—N1—C3—C4160.7 (2)
O2i—Pb1—O1—C2114.8 (3)C1—N1—C3—C2175.5 (3)
O1W—Pb1—O1—C291.8 (3)Pb1—N1—C3—C214.2 (4)
O3ii—Pb1—O1—C227.0 (4)O2—C2—C3—N1170.9 (3)
O1—Pb1—N1—C1163.4 (4)O1—C2—C3—N110.7 (5)
O3i—Pb1—N1—C138.2 (4)O2—C2—C3—C415.6 (6)
O2i—Pb1—N1—C1100.0 (4)O1—C2—C3—C4162.8 (4)
O1W—Pb1—N1—C1112.2 (4)C1—N2—C4—C30.7 (4)
O3ii—Pb1—N1—C128.1 (4)C1—N2—C4—C5176.1 (3)
O1—Pb1—N1—C39.3 (2)N1—C3—C4—N20.0 (4)
O3i—Pb1—N1—C3115.9 (3)C2—C3—C4—N2173.9 (4)
O2i—Pb1—N1—C354.1 (3)N1—C3—C4—C5174.3 (4)
O1W—Pb1—N1—C393.7 (3)C2—C3—C4—C50.4 (7)
O3ii—Pb1—N1—C3177.8 (3)Pb1iv—O3—C5—O4158.1 (3)
C3—N1—C1—N21.1 (4)Pb1v—O3—C5—O417.5 (5)
Pb1—N1—C1—N2154.8 (3)Pb1iv—O3—C5—C420.6 (5)
C4—N2—C1—N11.1 (5)Pb1v—O3—C5—C4161.2 (3)
Pb1iv—O2—C2—O1127.9 (3)N2—C4—C5—O427.2 (5)
Pb1iv—O2—C2—C353.9 (4)C3—C4—C5—O4146.4 (5)
Pb1—O1—C2—O2179.8 (3)N2—C4—C5—O3151.6 (4)
Pb1—O1—C2—C31.5 (5)C3—C4—C5—O334.8 (7)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x+1, y+1/2, z+1/2; (iv) x, y+1/2, z1/2; (v) x+1, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2iv0.86 (3)1.86 (3)2.708 (4)176 (6)
O1W—H1W2···O4ii0.85 (3)1.95 (3)2.705 (5)147 (4)
N2—H6···O1vi0.861.952.811 (4)174
Symmetry codes: (ii) x+1, y1/2, z+1/2; (iv) x, y+1/2, z1/2; (vi) x1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula[Pb(C5H2N2O4)(H2O)]
Mr379.30
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)7.0301 (14), 15.707 (3), 6.9680 (14)
β (°) 101.77 (3)
V3)753.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)22.39
Crystal size (mm)0.28 × 0.22 × 0.12
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionNumerical
(NUMABS; Higashi, 1995)
Tmin, Tmax0.007, 0.068
No. of measured, independent and
observed [I > 2σ(I)] reflections
7289, 1717, 1631
Rint0.037
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.049, 1.00
No. of reflections1717
No. of parameters124
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.59, 2.08

Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected bond lengths (Å) top
Pb1—O12.474 (3)Pb1—O1W2.739 (4)
Pb1—N12.491 (3)Pb1—O3ii2.758 (3)
Pb1—O3i2.547 (3)Pb1—O4iii2.822 (3)
Pb1—O2i2.598 (3)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x+1, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2iv0.86 (3)1.86 (3)2.708 (4)176 (6)
O1W—H1W2···O4ii0.85 (3)1.95 (3)2.705 (5)147 (4)
N2—H6···O1v0.861.952.811 (4)173.8
Symmetry codes: (ii) x+1, y1/2, z+1/2; (iv) x, y+1/2, z1/2; (v) x1, y+1/2, z1/2.
 

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